JP6874693B2 - Three-dimensional modeling material, manufacturing method of three-dimensional modeling material, and resin molded body - Google Patents

Description

The present invention relates to a three-dimensional molding material capable of obtaining a resin molded body having less warpage and excellent impact resistance and appearance, a method for producing the same, and a resin molded body formed by using the three-dimensional molding material.

In recent years, three-dimensional modeling technology (3D printing technology) has been attracting attention as a method for manufacturing a resin molded product. In particular, three-dimensional modeling equipment (3D printers) that use the Fused Deposition Modeling method are becoming cheaper and more widespread among general consumers.
In the Fused Deposition Modeling method, a thermoplastic resin is heated and melted and extruded from a nozzle to form a partial structure one layer at a time based on CAD data. Then, by repeating this and forming multiple layers, a resin molded body having a predetermined structure can be manufactured.

When a resin molded product is produced by the heat-melt lamination method, a filament made of PLA resin (polylactic acid resin) or ABS resin (acrylonitrile-butadiene-styrene copolymer) is generally used as the material.
For example, Patent Document 1 describes a three-dimensional modeling material obtained by blending a polylactic acid resin, a styrene resin, or the like.
This document also describes that by using the three-dimensional modeling material, a resin molded product having less warpage and easy surface polishing can be obtained.

International Publication No. 2015/37574 Pamphlet (US2016 / 0177878 A1)

As described in Patent Document 1, by using a three-dimensional modeling material containing a polylactic acid resin and other resin components, it is possible to produce a resin molded product having less warpage and easy surface polishing. ..
However, according to the study of the present inventor, it has been found that even when such a material is used, warpage occurs when the obtained resin molded product is placed under high humidity conditions for a long time.
Further, when ABS resin and an alicyclic structure-containing polymer were tried as the resin component, it was found that the problem of warpage and the problem of roughness of the surface of the resin molded product also occur when these resins are used.

The present invention has been made in view of the above circumstances, and is a three-dimensional molding material and a method for producing the same, which can obtain a resin molded body having less warpage and excellent impact resistance and appearance, and the above-mentioned three-dimensional molding. An object of the present invention is to provide a resin molded product formed by using a material.

In order to solve the above problems, the present inventor has diligently studied a material for three-dimensional modeling. As a result, by using a three-dimensional molding material containing an alicyclic structure-containing polymer as a resin component and having a reduced void fraction, a resin molded product having less warpage and excellent impact resistance and appearance. The present invention has been completed.

Thus, according to the present invention, the following three-dimensional modeling material [1], the method for producing the three-dimensional modeling material [2], and the resin molded product [3] are provided.
[1] A material for three-dimensional modeling containing an alicyclic structure-containing polymer and having a void fraction of 10% by volume or less.
[2] The production raw material containing the alicyclic structure-containing polymer is used at (glass transition temperature of the alicyclic structure-containing polymer −30 ° C.) to (glass transition temperature of the alicyclic structure-containing polymer -1 ° C.). The method for producing a three-dimensional modeling material according to [1], which comprises a step of drying.
[3] A resin molded product obtained by a fused deposition modeling method using the three-dimensional modeling material according to the above [1].

According to the present invention, a three-dimensional molding material and a manufacturing method thereof, which can obtain a resin molded body having less warpage and excellent impact resistance and appearance, and a resin molded body formed by using the three-dimensional molding material. Is provided.

It is a figure which shows the resin molded body manufactured in an Example.

The three-dimensional modeling material of the present invention is characterized by containing an alicyclic structure-containing polymer and having a void fraction of 10% by volume or less.

[Alicyclic structure-containing polymer]
The alicyclic structure-containing polymer contained in the three-dimensional modeling material of the present invention is a polymer having an alicyclic structure in the main chain and / or the side chain. Among them, those having an alicyclic structure in the main chain are preferable because a resin molded product having excellent mechanical strength, heat resistance and the like can be easily obtained.
Examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. Of these, a cycloalkane structure is preferable because it is easy to obtain a resin molded product having excellent mechanical strength, heat resistance, and the like.
The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15. When the number of carbon atoms constituting the alicyclic structure is within these ranges, it becomes easy to obtain a resin molded product in which characteristics such as mechanical strength and heat resistance are more highly balanced.

The ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer can be appropriately selected according to the purpose of use. The ratio of the repeating unit is usually 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more with respect to all the repeating units. When the ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is 30% by weight or more, it becomes easy to obtain a resin molded product having excellent heat resistance, transparency and the like. The remainder of the polymer containing an alicyclic structure other than the repeating unit having an alicyclic structure is not particularly limited and is appropriately selected according to the purpose of use.

The weight average molecular weight (Mw) of the alicyclic structure-containing polymer is not particularly limited, but is usually 5,000 to 500,000, preferably 8,000 to 200,000, and more preferably 10,000 to 100,000. Is. When the weight average molecular weight (Mw) of the alicyclic structure-containing polymer is within these ranges, the mechanical strength of the resin molded product and the workability in producing the resin molded product are more highly balanced. ..
The molecular weight distribution (Mw / Mn) of the alicyclic structure-containing polymer is not particularly limited, but is usually 1.0 to 4.0, preferably 1.0 to 3.0, and more preferably 1.0 to 2. It is 5.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alicyclic structure-containing polymer can be determined according to the method described in Examples.

The glass transition temperature (Tg) of the alicyclic structure-containing polymer is not particularly limited, but is usually 100 to 200 ° C, preferably 100 to 170 ° C.
When the glass transition temperature (Tg) of the alicyclic structure-containing polymer is 100 ° C. or higher, it becomes easy to obtain a resin molded product having excellent heat resistance. Further, the resin composition containing the alicyclic structure-containing polymer having a glass transition temperature (Tg) of 200 ° C. or lower has sufficient fluidity at the time of melting and is excellent in moldability.
The glass transition temperature (Tg) can be measured based on JIS K 6911.

Specific examples of the alicyclic structure-containing polymer include (1) norbornene-based polymer, (2) monocyclic cyclic olefin-based polymer, (3) cyclic conjugated diene-based polymer, and (4) vinyl alicyclic hydrocarbon. Examples include hydrogen-based polymers. Among these, a norbornene-based polymer is preferable because a resin molded product having excellent heat resistance and mechanical strength can be easily obtained.
In addition, in this specification, these polymers mean not only a polymerization reaction product but also the hydrogenated product thereof.

(1) Norbornene-based polymer The norbornene-based polymer is a polymer or a hydrogenated product thereof obtained by polymerizing a norbornene-based monomer which is a monomer having a norbornene skeleton.
Examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization thereof, and a ring-opening polymer thereof. Examples thereof include an addition polymer of a norbornene-based monomer, and an addition polymer of a norbornene-based monomer and another monomer copolymerizable therewith.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (meaning those having a substituent on the ring), tricyclo [4.3.0]. ^1,6 . 1 ^2,5] deca-3,7-diene (trivial name: dicyclopentadiene) and derivatives thereof, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] Tetradeca-3,5,7,12-tetraene (methanotetrahydrofluorene, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] deca-3-ene, 1,4- Metano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.1, ^2,5 . ^{17 and 10} . 0] Dodeca-3-ene (common name: tetracyclododecene) and its derivatives can be mentioned.

Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, an alkylidene group and the like.
Examples of the norbornene-based monomer having a substituent include 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-en and the like.
These norbornene-based monomers can be used alone or in combination of two or more.

Examples of other monomers ring-opening copolymerizable with norbornene-based monomers include monocyclic cyclic olefin-based monomers such as cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. Examples of these substituents include those similar to those shown as substituents for norbornene-based monomers.

Other monomers that can be additionally copolymerized with the norbornene-based monomer include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene, and derivatives thereof. Cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, and derivatives thereof; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadien Non-conjugated diene such as; Among these, α-olefins are preferable, and ethylene is particularly preferable. Examples of these substituents include those similar to those shown as substituents for norbornene-based monomers.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization thereof, comprises a known ring-opening polymerization of a monomer component. It can be obtained by polymerization in the presence of a catalyst. Examples of the ring-opening polymerization catalyst include a catalyst composed of a metal halide such as ruthenium and osmium, a nitrate or an acetylacetone compound, and a reducing agent, or a metal halide or acetylacetone such as titanium, zirconium, tungsten and molybdenum. Examples thereof include a catalyst composed of a compound and an organoaluminum compound.
A ring-opening polymer hydrogenated additive of a norbornene-based monomer is usually obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization solution of the ring-opening polymer and carbon-carbon unsaturated. It can be obtained by hydrogenating the bond.

An addition polymer of a norbornene-based monomer or an addition polymer of a norbornene-based monomer and another monomer copolymerizable therewith contains a monomer component in the presence of a known addition polymerization catalyst. It can be synthesized by polymerizing. Examples of the addition polymerization catalyst include a catalyst composed of a titanium, zirconium or vanadium compound and an organoaluminum compound.

Among these norbornene-based polymers, a ring-opening polymer hydrogenated additive of a norbornene-based monomer is preferable because a resin molded product having excellent heat resistance, mechanical strength and the like can be easily obtained.

(2) Monocyclic Cyclic Olefin Polymers Examples of the monocyclic cyclic olefin-based polymers include addition polymers of monocyclic cyclic olefin-based monomers such as cyclohexene, cycloheptene, and cyclooctene.
The method for synthesizing these addition polymers is not particularly limited, and known methods can be appropriately used.

(3) Cyclic-conjugated diene-based polymer Examples of the cyclic-conjugated diene-based polymer include polymers obtained by addition-polymerizing cyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene with 1,2- or 1,4-addition polymerization. Examples thereof include the hydrogen additive.
The method for synthesizing these addition polymers is not particularly limited, and known methods can be appropriately used.

(4) Vinyl-Aromatic Hydrocarbon-based Polymer Examples of the vinyl-aromatic hydrocarbon-based polymer include a polymer of a vinyl alicyclic hydrocarbon-based monomer such as vinylcyclohexene and vinylcyclohexane, and hydrogenation thereof. Products; Hydrocarbons of the aromatic ring portion of a polymer of a polymer of vinyl aromatic monomers such as styrene and α-methylstyrene; and the like. Further, it may be a copolymer of a vinyl alicyclic hydrocarbon-based monomer or a vinyl aromatic monomer and another monomer copolymerizable with these monomers. Examples of such copolymers include random copolymers and block copolymers.
The method for synthesizing these polymers is not particularly limited, and known methods can be appropriately used.

The three-dimensional modeling material of the present invention may contain components other than the alicyclic structure-containing polymer.

Ingredients other than the alicyclic structure-containing polymer include polymers other than the alicyclic structure-containing polymer, antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, plasticizers, antistatic agents, and acid supplements. Additives such as.

Examples of the polymer other than the alicyclic structure-containing polymer include a soft polymer and a terpene phenol resin.

The soft polymer is a polymer described in JP-A-2006-124580 and the like, which usually has a Tg of 30 ° C. or lower, and when a plurality of Tg are present, at least the lowest Tg is 30 ° C. or lower. It is a polymer. Among such soft polymers, those having a melt mass flow rate (MFR) of 10 g / 10 min to 100 g / 10 min at 230 ° C. and 21.18 N measured according to JIS K 7210 are preferable.

Examples of the soft polymer include liquid polyethylene, polypropylene, poly-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, ethylene / propylene / diene copolymer (EPDM), and ethylene. -Olefin soft polymers such as propylene / styrene copolymers; isobutylene soft polymers such as polyisobutylene, isobutylene / isoprene rubber, isobutylene / styrene copolymers; polybutadiene, polyisoprene, butadiene / styrene random copolymers, Isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, butadiene / styrene / block copolymer, styrene / butadiene / styrene / block copolymer, isoprene / styrene copolymer Diene-based soft polymers such as styrene / isoprene / styrene / block copolymers; silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, and dihydroxypolysiloxane; polybutylacrylate, polybutylmethacrylate, polyhydroxyethyl Soft polymers composed of α, β-unsaturated acids such as methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate / styrene copolymers; polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, vinyl acetate / styrene copolymers, etc. Soft polymers composed of unsaturated alcohols and amines or acyl derivatives thereof or acetal; epoxy-based soft copolymers such as polyethylene oxide, polypropylene oxide, epichlorohydrin rubber, etc .; vinylidene fluoride-based rubber, ethylene tetrafluoride-propylene rubber, etc. Fluorine-based soft copolymers; Examples thereof include soft polymers such as natural rubbers, polypeptides, proteins, polyester-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers. These soft polymers may have a crosslinked structure, or may have a functional group introduced by a modification reaction.
Each of these soft polymers can be used alone or in combination of two or more.

When the three-dimensional modeling material of the present invention contains a soft polymer, the content thereof is usually 0.01 to 50% by weight, preferably 0.1 to 30% by weight, based on the alicyclic structure-containing polymer. %. If the content of the soft polymer is too large, the transparency of the obtained resin composition may decrease.

The terpene phenol resin is a polymerization reaction product of a terpene compound and phenols. In the terpene phenol resin, for example, 1 mol of a terpene compound and 0.1 to 15 mol of phenols are subjected to a cationic polymerization reaction under a Friedel-Crafts catalyst at a temperature of -10 to + 120 ° C. for 0.5 to 20 hours. Can be manufactured.

Examples of terpine compounds include milsen, aloosine, osimene, α-pinene, β-pinene, dipentene, limonene, α-ferandrene, α-terpinene, γ-terpinene, terpineol, 1,8-cineol, 1,4-cineol, Examples thereof include α-terpineol, β-terpineol, γ-terpineol, camphene, tricyclene, sabinene, paramentadiens, and curenes.

Examples of phenols include phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A and the like.

Examples of the Friedel-Crafts catalyst include zinc chloride, titanium tetrachloride, tin chloride, aluminum chloride, boron trifluoride, iron chloride, antimony trichloride and the like.

Further, a hydrogenated terpene resin oligomer or the like obtained by hydrogenating a terpene phenol resin can also be used as the terpene phenol resin.
A commercially available product may be used as the terpene phenol resin. Examples of commercially available products include the Polystar series and Mighty Ace series manufactured by Yasuhara Chemical Co., Ltd.

When the three-dimensional modeling material of the present invention contains a terpene phenol resin, the content thereof is usually 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the alicyclic structure-containing polymer. is there. If the content of the terpene phenol resin is too large, the thermal stability of the obtained resin molded product may decrease.

Examples of the antioxidant include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and the like.

Examples of the phenolic antioxidant include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2'-methylenebis (6-t-butyl-4-methylphenol), and 4,4'. -Buchilidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), α-tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, [pentaerythritol tetrakis [3- (3,5-di) -T-Butyl-4-hydroxyphenyl) propionate]] and the like.

Phosphorus-based antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditershally butylphenyl) pentaerythritol diphosphite, tris (2,4-ditershally butylphenyl) phosphite, and tetrakis (2). , 4-Dither Shari Butylphenyl) 4,4'-biphenyldiphosphite, trinonylphenylphosphite and the like.

Examples of the sulfur-based antioxidant include distearylthiodipropionate and dilaurylthiodipropionate.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, bezoate-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, acrylate-based ultraviolet absorbers, metal complex-based ultraviolet absorbers, and the like.
Examples of the light stabilizer include hindered amine-based light stabilizers.

Near-infrared absorbers include cyanine-based near-infrared absorbers; pyririum-based infrared absorbers; squarylium-based near-infrared absorbers; croconium-based infrared absorbers; azulenium-based near-infrared absorbers; phthalocyanine-based near-infrared absorbers; dithiol metal complex System Near-infrared absorber; Naftquinone-based near-infrared absorber; Anthraquinone-based near-infrared absorber; Indophenol-based near-infrared absorber; Aji-based near-infrared absorber;
Examples of the plasticizer include a phosphoric acid triester-based plasticizer, a fatty acid monobasic acid ester-based plasticizer, a dihydric alcohol ester-based plasticizer, an oxyacid ester-based plasticizer, and the like.
Examples of the antistatic agent include fatty acid esters of polyhydric alcohols.
Examples of the acid supplement include magnesium oxide, zinc stearate and the like.

The content of these components can be appropriately determined according to the purpose. The content is usually in the range of 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on the alicyclic structure-containing polymer.

The void fraction of the three-dimensional modeling material of the present invention is 10% by volume or less, preferably 0 to 5% by volume, and more preferably 0 to 2% by volume.
When a resin molded product is manufactured using a three-dimensional molding material containing an alicyclic structure-containing polymer, the surface of the resin molded product tends to be roughened. In the present invention, by reducing the void fraction of the three-dimensional modeling material containing the alicyclic structure-containing polymer, it is possible to produce a resin molded product having an excellent appearance with suppressed surface roughness. ..
The void fraction of the three-dimensional modeling material can be determined according to the method described in Examples.

A three-dimensional modeling material having a low void fraction can be obtained by subjecting a raw material for producing the three-dimensional modeling material to a drying treatment, as will be described later.

In the three-dimensional molding material of the present invention, each component is mixed as necessary to obtain a manufacturing raw material, and then the manufacturing raw material is subjected to a drying treatment, and then the manufacturing raw material is melt-molded into a predetermined shape. Can be obtained by doing.

Examples of the mixing method for obtaining a production raw material include a method of mixing each component in an appropriate solvent and a method of kneading in a molten state.
The kneading can be performed by using a melt kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a feeder ruder, and a high shearing machine. The kneading temperature is preferably in the range of 180 to 400 ° C, more preferably 200 to 350 ° C. At the time of kneading, each component may be added all at once and kneaded, or may be kneaded while being added in several times.
The shape of the raw material is not particularly limited, but pelletized according to a conventional method is preferably used.

The drying conditions of the production raw material are not particularly limited, but the drying temperature is usually (Tgc-30 ° C.) to (Tgc-1 ° C.), where Tgc (° C.) is the glass transition temperature of the alicyclic structure-containing polymer. Preferably, it is (Tgc-25 ° C.) to (Tgc-5 ° C.). The drying time is usually 4 to 24 hours, preferably 4 to 12 hours. Drying may be carried out under normal pressure (pressure equal to atmospheric pressure) or under reduced pressure, but is preferably 1 to 100 kPa, more preferably 1 to 50 kPa.

A known method can be used when melt-molding the dried production raw material.
For example, the dried production raw material is put into an extruder, melt-kneaded, and then the molten resin is continuously discharged from a spinning nozzle connected to the extruder and cooled to form a filament-like tertiary. The original modeling material can be obtained.

The diameter of the filament-shaped three-dimensional modeling material is not particularly limited, but is usually 1.0 to 2.5 mm.

In addition, the dried production raw material is put into an extruder, melt-kneaded, then extruded into a rod shape from the extruder, cooled, and then cut into an appropriate length with a strand cutter to form a pellet-shaped three-dimensional shape. A molding material can be obtained.

The three-dimensional modeling material of the present invention is used when producing a resin molded product by the Fused Deposition Modeling method.
Fused Deposition Modeling is a type of three-dimensional modeling technology. While heating and melting a three-dimensional modeling material and extruding it from a nozzle, a partial structure is formed layer by layer based on CAD data, and this is repeated to create multiple layers. By doing so, a resin molded body having a predetermined structure is manufactured.
When producing a resin molded product using the three-dimensional modeling material of the present invention, a commercially available 3D printer of the heat-melting lamination method can be used.

Since the three-dimensional molding material of the present invention contains an alicyclic structure-containing polymer, the resin molded product obtained by the Fused Deposition Modeling method using the three-dimensional molding material of the present invention has small warpage and impact resistance. Excellent in sex.
Further, since the three-dimensional molding material of the present invention contains an alicyclic structure-containing polymer and has a void content of 10% by volume or less, the three-dimensional molding material of the present invention is used for fused deposition modeling. The resin molded product obtained by the method has excellent appearance with suppressed surface roughness.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. In the following, "parts" and "%" are based on weight unless otherwise specified.

The methods for measuring various physical properties are as follows.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn)
Gel permeation chromatography (GPC) using cyclohexane as an eluent was performed at 40 ° C., and the weight average molecular weight (Mw) and the number average molecular weight were determined as standard polyisoprene equivalent values.
As a measuring device, HLC8120GPC (manufactured by Tosoh Corporation) was used.
As the standard polyisoprene, standard polyisoprene (Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000, a total of 10 points, all manufactured by Tosoh Corporation) was used.
The sample was prepared by heating and dissolving the measurement sample in cyclohexane at 40 ° C. so that the sample concentration was 4 mg / ml.
The measurement was performed under the conditions of TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL (all manufactured by Tosoh Corporation) connected in series at a flow velocity of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C. It was.

(2) Hydrogenation rate The hydrogenation rate in the hydrogenation reaction was calculated based on the measurement results ^{of 1 H-NMR measured in a deuterated chloroform solvent.}

(3) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the resin composition was measured based on JIS K 6911 using a differential scanning calorimeter (DSC6220SII, manufactured by Nanotechnology).

(4) The density of the three-dimensional modeling material (filament) was measured using a void fraction specific gravity measuring device (Type A, manufactured by Shibayama Kagaku Kikai Seisakusho). Then, using the obtained measured density, the void fraction was calculated by the following formula.

(5) Surface Roughness of Resin Mold The surface roughness (Ra) (μm) of the surface of the resin molded product in the range of 200 μm × 200 μm was measured using a color 3D laser microscope (manufactured by KEYENCE CORPORATION).

(6) Warpage of the resin molded body Place the 3a1, 3b1 surface portions of the resin molded body on a flat table, and use a clearance gauge to warp the resin molded body (3a1, 3b1 surfaces of the resin molded body and the flat table). The maximum value of the space between them) was measured.

(7) Warpage of resin molded product after environmental test The resin molded product is placed in a constant temperature and humidity chamber set at a temperature of 60 ° C. and a relative humidity of 90%, taken out after one week, and the amount of warpage by the method described in (6). Was measured.

(8) Impact resistance The resin molded product was dropped from a height of 1.5 m onto the concrete floor. After repeating this 10 times, the presence or absence of fracture or deformation was examined by visual observation, and the impact resistance was evaluated according to the following criteria.
◯: After 10 drop tests, the resin molded product was not destroyed and was not deformed.
Δ: After 10 drop tests, the resin molded product was not destroyed, but was deformed.
X: The resin molded product was destroyed within 10 times.

[Manufacturing Example 1]
250 parts of dehydrated cyclohexane was placed in a reactor at room temperature (25 ° C.) with a nitrogen atmosphere inside, and 0.82 parts of 1-hexene, 0.15 parts of dibutyl ether and 0.30 parts of triisobutylaluminum were further added. And mixed. Then, while keeping the inside of the reactor at 45 ° C., ^{85 parts of tricyclo [4.3.0.1 2,5} ] deca-3-ene (DCP), 8-ethyl-tetracyclo [4.4.0.1 ^{2]. , 5} . ^{17 and 10} ] 15 parts of dodeca-3-ene (ETD) and 40 parts of a 0.7% toluene solution of tungsten hexachloride were continuously added over 2 hours to carry out a polymerization reaction. Next, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to the polymerization reaction solution to inactivate the polymerization catalyst and stop the polymerization reaction. The polymerization conversion rate was 100%.

The obtained polymerization reaction solution was transferred to a pressure-resistant hydrogenation reactor, and 5 parts of a diatomaceous earth-supported nickel catalyst (G-96D, nickel-supporting rate 58%, manufactured by Nissan Gardler) and 100 parts of cyclohexane were added, and 150 parts were added. The reaction was carried out at ° C. and a hydrogen pressure of 4.4 MPa for 8 hours. The obtained reaction solution is pressure-filtered at a pressure of 0.25 MPa using a pressure filter (Fundafilter, manufactured by IHI) using Radiolite # 500 (manufactured by Showa Kagaku Kogyo Co., Ltd.) as a filtration bed to hydrogenate. The addition catalyst was removed to obtain a solution containing a colorless and transparent norbornene-based ring-opening polymer hydrogenated product.
The weight average molecular weight (Mw) of the obtained norbornene-based ring-opening polymer hydrogenated product is 41,000, the molecular weight distribution (Mw / Mn) is 3.4, the hydrogenation rate is 99.4%, and the branching index is 1. It was 00.

Next, in the solution containing the norbornene-based ring-opening polymer hydrogenated additive obtained above, 0.50 part of the antioxidant: pentaerythritol tetrakis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by BASF) was added and dissolved. The obtained solution is sequentially filtered through a filter (Zeter Plus filter 30H, pore size 0.5 to 1 μm, manufactured by Kunault Filter Co., Ltd.), and further filtered through another metal fiber filter (pore diameter 0.4 μm, manufactured by Nichidai Corporation). It was filtered to remove minute solids.
Then, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), the solvent cyclohexane and other volatile components were removed from the obtained filtrate under the conditions of a temperature of 270 ° C. and a pressure of 1 kPa or less, and the residue was left as it was. It was melted. This melt was extruded into a strand shape from a die directly connected to a concentration dryer, cooled and pelletized to obtain a resin composition (A) containing a norbornene-based ring-opening polymer hydrogenated additive.
The glass transition temperature of this resin composition (A) was 105 ° C.

[Example 1]
The resin composition (A) obtained in Production Example 1 was dried in a vacuum dryer at 85 ° C. for 5 hours, and then the hopper was replaced with nitrogen to set the temperature to 200 ° C. in a single-screw melt extruder. Was supplied and melted. The melt was extruded, and while being taken up by the first roller, it was guided to a cooling bath set to a temperature of 40 ° C. and cooled to obtain a filament 1 having a diameter of 1.8 mm. The void fraction of filament 1 was 0.3%.

Using the obtained filament 1, the resin molded product 1 shown in FIG. 1 was obtained using a 3D printing device in which the nozzle temperature was set to 210 ° C.
In FIG. 1, the broken lines represented by 100a, 100b, 110a, 110b and the like are virtual lines for explaining the structure of the resin molded body 1. What is shown by these broken lines is a cube, the length of 100a is 50 mm, the length of 100b is 50 mm, the length of 110a is 50 mm, and the length of 110b is 50 mm. 3a1, 3a2, 3a3, 3a4, 3b1, 3b2, 3b3, and 3b4 are cylinders having a diameter of 5 mm, respectively, and the angle θa and the angle θb are 45 °.
Various tests were performed on the obtained resin molded product 1. The results are shown in Table 1.

[Example 2]
After mixing 80 parts of the resin composition (A) obtained in Production Example 1 and 20 parts of a hydrogenated styrene / butadiene / styrene / block copolymer (SEBS: Toughtec H1051, manufactured by Asahi Kasei Chemicals Co., Ltd.) with a blender, The mixture was dried in a vacuum dryer at 85 ° C. for 5 hours.
Filament 2 was obtained in the same manner as in Example 1 except that this mixture was used in place of the dried resin composition (A). The void fraction of filament 2 was 0.2%.
Using the obtained filament 2, a resin molded product 2 was obtained in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Comparative Example 1]
Filament 3 was obtained in the same manner as in Example 1 except that the resin composition (A) was not dried in Example 1. The void fraction of filament 3 was 12%.
Using the obtained filament 3, a resin molded product 3 was obtained in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Comparative Example 2]
Filament 4 was obtained in the same manner as in Example 1 except that a polylactic acid resin (Ecodia V911X51, manufactured by Toray Industries, Inc.) was used instead of the resin composition (A) in Example 1. The void fraction of filament 4 was 0.1%.
Using the obtained filament 4, a resin molded product 4 was obtained in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Comparative Example 3]
After mixing 100 parts of the polylactic acid resin used in Comparative Example 2 and 150 parts of an acrylic elastomer (Metabrene S-2001, manufactured by Mitsubishi Rayon Co., Ltd.) with a blender, this mixture was mixed in a vacuum dryer at 80 ° C. for 5 hours. It was dry.
Filament 5 was obtained in the same manner as in Example 1 except that this mixture was used in place of the dried resin composition (A). The void fraction of filament 5 was 0.1%.
Using the obtained filament 5, a resin molded product 5 was obtained in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

[Comparative Example 4]
Filament 6 was obtained in the same manner as in Example 1 except that ABS resin (Denka ABSQF, manufactured by Denka Co., Ltd.) was used instead of the resin composition (A) in Example 1. The void fraction of filament 6 was 0.1%.
Using the obtained filament 6, a resin molded product 6 was obtained in the same manner as in Example 1, and various tests were performed. The results are shown in Table 1.

The following can be seen from Table 1.
The resin molded products of Examples 1 and 2 formed by using a three-dimensional molding material containing an alicyclic structure-containing polymer and having a void fraction of 10% by volume or less have a small surface roughness value. No warpage is seen and it has excellent impact resistance.
On the other hand, in Comparative Example 2 using the polylactic acid resin, the resin molded product was warped after the environmental test, and the impact resistance was inferior.
The problem of impact resistance in the polylactic acid resin is improved by including an elastomer component as shown in Comparative Example 3, but in this case, the warp of the resin molded product after the environmental test becomes larger.
Further, the resin molded product of Comparative Example 4 using ABS resin has a large warp.
These problems of warpage and impact resistance can be improved by using an alicyclic structure-containing polymer as shown in Comparative Example 1, but in a three-dimensional molding material containing an alicyclic structure-containing polymer. When the void fraction is large, the value of the surface roughness of the resin molded product becomes large.

Claims (4)

A material for three-dimensional modeling containing a norbornene-based polymer and having a void fraction of 10% by volume or less. The method for producing a three-dimensional modeling material according to claim 1, further comprising a step of drying a production raw material containing a norbornene-based polymer and a step of melt-molding the dried production raw material. The three-dimensional modeling according to claim 2 , further comprising a step of drying at (glass transition temperature of the norbornene-based polymer −30 ° C.) to (glass transition temperature of the norbornene-based polymer-1 ° C.). Material manufacturing method. A method for producing a resin molded product by a fused deposition modeling method using the three-dimensional modeling material according to claim 1.

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